Mixtures of reactive dyes and their use

ABSTRACT

Dye mixtures, which comprise at least one dye of formula (1) together with at least one dye of formula (2), wherein R1, R2, R4 and R5 are each independently of one another hydrogen or unsubstituted or substituted C1-C4alkyl, (R3)0-2 is 0 to 2 identical or different substituents selected from the group consisting of C2-C4halogen alkanoylamino, C1-C4alkyl or C1-C4alkoxy, A1 and A2 are each independently of the other an unsubstituted or substituted phenylene radical or a C1-C8alkylene radical which may be interrupted by oxygen, D is a radical of formula (3) or (4) wherein is (R6)0-2 0 to 2 identical or different substituents selected from the group consisting of halogen, C2-C4alkanoylamino, C1-C4alkyl and C1-C4alkoxy, X1 and X2 are halogen, and Y1 and Y2 are each independently of the other a fiber-reactive radical of formula: -SO2-Z (5a): -CONH-(CH2)m-SO2-Z (5b); -NH-CO-CH(Hal)-CH2-Hal (5c).

The present invention relates to novel improved reactive dye mixtureswhich are particularly suitable for dyeing or printingnitrogen-containing or hydroxyl group-containing fibre materials byprocesses which are customarily used for reactive dyes and which yielddyeings which are fast to wet treatment and light; and to a process forthe preparation of these dye mixtures, as well as to their use fordyeing or printing textile materials.

Accordingly, this invention relates to dye mixtures, which comprise atleast one dye of formula (1)

together with at least one dye of formula (2)

wherein

R₁, R₂, R₄ and R₅ are each independently of one another hydrogen orunsubstituted or substituted C₁-C₄alkyl,

(R₃)₀₋₂ is 0 to 2 identical or different substituents selected from thegroup consisting of halogen, C₂-C₄alkanoylamino, C₁-C₄alkyl andC₁-C₄alkoxy,

A₁ and A₂ are each independently of the other an unsubstituted orsubstituted phenylene radical or a C₁-C₈alkylene radical which may beinterrupted by oxygen,

D is a radical of formula (3) or (4)

wherein

(R₆)₀₋₂ is 0 to 2 identical or different substituents selected from thegroup consisting of halogen, C₂-C₄alkanoylamino, C₁-C₄alkyl andC₁-C₄alkoxy,

X₁ and X₂ are halogen, and

Y₁ and Y₂ are each independently of the other a fibre-reactive radicalof formula (5a), (5b), (5c) or (5d)

—SO₂—Z  (5a),

—CONH—(CH₂)_(m)—SO₂—Z  (5b),

—NH—CO—CH(Hal)—CH₂Hal  (5c) or

—NH—CO—C(Hal)═CH₂  (5d),

wherein

m is the number 2, 3 or 4,

Hal is halogen, and

Z is vinyl or a radical —CH₂—CH₂—U, and U is a group which may be splitoff with alkali.

R₁, R₂, R₄ and R₅ defined as C₁-C₄alkyl may suitably be eachindependently of one another typically methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyland, particularly preferably, methyl. The cited alkyl radicals may beunsubstituted or substituted by e.g. hydroxy, sulfo, sulfato, cyano orcarboxyl. The corresponding unsubstituted alkyl radicals are preferred.

R₃ and R₆ defined as C₁-C₄alkyl may suitably be each independently ofthe other e.g. methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,tert-butyl or isobutyl, preferably methyl or ethyl and, particularlypreferably, methyl.

R₃ and R₆ defined as C₁-C₄alkoxy may suitably be each independently ofthe other e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy orisobutoxy, preferably methoxy or ethoxy and, particularly preferably,methoxy.

R₃ and R₆ defined as C₂-C₄alkanoylamino may suitably be eachindependently of the other e.g. acetylamino or propionylamino and,preferably, acetylamino.

R₃ and R₆ defined as halogen may suitably be each independently of theother e.g. fluoro, chloro or bromo, preferably chloro or bromo and,particularly preferably, chloro.

Hal is, for example, fluoro, chloro or bromo, preferably chloro orbromo, particularly preferably bromo.

m in the fibre-reactive group of formula (5b) is preferably the number2.

X₁ and X₂ defined as halogen may suitably be each independently of theother e.g. fluoro, chloro or bromo.

Preferred dye mixtures are those, wherein

R₁, R₂, R₄ and R₅ are each independently of one another hydrogen orC₁-C₄alkyl, preferably hydrogen.

In the novel dye mixtures, D defined as a radical of formula (3) is, forexample, a radical of formula

preferably a radical of formula (3.3).

In the novel dye mixtures, D defined as a radical of formula (4) is, forexample, a radical of formula

preferably a radical of formula (4.1) or (4.6) and, particularlypreferably, a radical of formula (4.1).

In a preferred embodiment of the dye mixtures of this invention, Ddefined as a radical of formula (3) is a radical of formula (3a)

and, defined as a radical of formula (4), a radical of formula (4a)

wherein

R₆ is hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy, preferably hydrogen, methyl,ethyl, methoxy or ethoxy, more preferably methyl or methoxy and, veryparticularly preferably, methoxy.

Preferred dye mixtures are those, wherein X₁ and X₂ are eachindependently of the other fluoro or chloro, preferably chloro.

The meanings of X₁ and X₂ in the novel dye mixtures are preferablyidentical.

Suitable leaving groups U are, for example, —Cl, —Br, —F, —OSO₃H,—SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl or—OSO₂—N(C₁-C₄alkyl)₂. U is preferably a group of formula —Cl, —OSO₃H,—SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, more preferably —Cl or —OSO₃Hand, particularly preferably, —OSO₃H.

If A₁ or A₂ in the novel dye mixtures are defined as an unsubstituted orsubstituted phenylene radical, suitable substituents are eachindependently of the other e.g. identical or different radicals selectedfrom the group consisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy and sulfo,preferably of C₁-C₄alkyl, C₁-C₄alkoxy and sulfo and, particularlypreferably, of methyl, methoxy and sulfo. The fibre-reactive Y₁ or Y₂are in this case each independently of the other radicals of formula(5a), (5b), (5c) or (5d), preferably of formula (5a) or (5b), whichradicals have the above-cited meanings and preferred meanings.

A₁ or A₂ defined as a C₁-C₈alkylene radical which may be interrupted byoxygen may suitably be each independently of the other e.g. ethylene,propylene, isopropylene, butylene, isobutylene, —(CH₂)₂—O—(CH₂)₂—,—(CH₂)₃—O—(CH₂)₂— or —(CH₂)₃—O—(CH₂)₃—. The fiber-reactive Y₁ or Y₂ arein this case preferably a radical of formula (5a), which has theabove-cited meanings and preferred meanings. A₁ and A₂ are preferably aC₁-C₆alkylene radical which is correspondingly interrupted and,particularly preferably, a C₁-C₄alkylene radical such as ethylene or—(CH₂)₂—O—(CH₂)₂—.

In a preferred embodiment of the novel dye mixtures, the radicals offormulae —A₁—Y₁ and A₂—Y₂ in the dyes of formulae (1) and (2) are eachindependently of the other a radical of formula (6a), (6b) or (6c)

wherein

(R₇)₀₋₂ is 0 to 2 identical or different substituents selected from thegroup consisting of sulfo, methyl or methoxy,

Y is α,β-dibromopropionylamino or α-bromoacryloylamino, and

Z₁ and Z₂ are each independently of the other vinyl, β-chloroethyl orβ-sulfatoethyl, preferably vinyl or β-sulfatoethyl.

In the radicals of formula (6a), the fibre-reactive group —SO₂—Z₁ ispreferably in 4-position.

R₇ is preferably hydrogen.

In the radicals of formula (6b), the fibre-reactive group—CO—NH—(CH₂)₂—SO₂—Z₂ is preferably in 3-position. The radical of formula(6b) preferably does not contain any sulfo group at the benzene ring.

In a particularly preferred embodiment of the novel dye mixtures, theradicals of formulae —A₁—Y₁ and A₂—Y₂ in the dyes of formulae (1) and(2) are each independently of the other a radical of formula (6a) or(6b), preferably, of formula (6a), which radicals have the above-citedmeanings and preferred meanings.

—A₁—Y₁ and A₂—Y₂ in the novel dye mixtures are preferably identical.

Preferred dye mixtures are those, which comprise at least one dye offormula (1a)

together with at least one dye of formula (2a)

wherein

R₃ is hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy, preferably hydrogen, methylor methoxy, D is a radical of formula (3a) or (4a),

X₁ and X₂ are each independently of the other fluoro or chloro, and

—A₁—Y₁ and A₂—Y₂ are each independently of the other a radical offormula (6a) or (6b), which radicals have the above-cited meanings andpreferred meanings.

In the dyes of formulae (1a) and (2a) of the novel dye mixtures, theaminotriazinyl radical of formulae

is preferably bound in 3-position to the coupling component of the azochromophore.

In a particularly preferred embodiment of this invention, the novel dyemixtures comprise at least one dye of formula (1b)

together with at least one dye of formula (2b)

wherein

R₃ is hydrogen or methyl, preferably hydrogen, and

X₁ and X₂ and —A₁—Y₁ and A₂—Y₂ each have the above meanings andpreferred meanings.

In another particularly preferred embodiment of this invention, thenovel dye mixtures comprise at least one dye of formula (1c)

together with at least one dye of formula (2c)

wherein

X₁ and X₂ and —A₁—Y₁ and A₂—Y₂ each have the above meanings andpreferred meanings.

This invention also relates to a process for the preparation of thenovel dye mixtures, which comprises reacting a compound of formula

and a compound of formula

with cyanuric halide and an amine selected from the group consisting offormulae (9) and

n any sequence with each other,

R₁, R₂, R₃, R₄, R₅, A₁, A₂, D, Y₁ and Y₂ having the above meanings andpreferred meanings.

As the individual process steps described above can be carried out indifferent sequence, or also simultaneously, different process variantsare possible. The reaction is normally carried out stepwise, thesequence of the simple reactions between the individual reactioncomponents preferably depending on the particular conditions. Thus, forexample, about one molar equivalent of an amine of formula (9) and/or(10) is reacted with about one molar equivalent of cyanuric halide andthe resulting product is then condensed with about one molar equivalentof a mixture of the compounds of formulae (7) and (8). In anotherprocess variant e.g. about one molar equivalent of a mixture of thecompounds of formulae (7) and (8) is reacted with about one molarequivalent of cyanuric halide and the resulting mixture is thencondensed with about one molar equivalent of an amine of formula (9)and/or (10). The ratio of the dyes of formulae (1) and (2) in the noveldye mixtures depends in this case on the mixture ratio of the compoundsof formulae (7) and (8).

The individual condensation reactions are carried out, for example, byprocesses known per se, usually in an aqueous solution and in thetemperature range from e.g. 0 to 50° C., preferably from 0 to 10° C.,and at a pH from e.g. 3 to 10, preferably from 3 to 7.

Suitable cyanuric halides are, for example, cyanuric chloride andcyanuric fluoride, preferably cyanuric chloride.

After the synthesis, conversion reactions may also be carried out, forexample an elimination reaction. The novel dye mixtures containingβ-sulfatoethylsulfonyl radicals or α,β-dihalopro-pionylamino radicalsmay, for example, be treated with a base, such as sodium hydroxide, thesulfatoethylsulfonyl radicals converting into vinyl sulfonyl radicalsand the α,β-dihalopro-pionylamino radicals converting intoα-haloacryloylamino radicals.

The compounds of formulae (7), (8), (9) and (10) are known or may beprepared in analogy to known compounds.

The novel dye mixtures can, for example, also be prepared by mixing theindividual dyes of formulae (1) and (2). This mixing process istypically carried out in suitable mills, e.g. ball or pin mills, and inkneaders or mixers.

The dyes of formulae (1) and (2) of the novel dye mixtures are usedeither in the form of their free acids or, preferably, in the form oftheir salts. Suitable salts are, for example, the alkali metal, alkalineearth metal or ammonium salts or the salts of an organic amine. Examplesto be mentioned are the sodium, lithium, potassium or ammonium salts orthe salt of the mono-, di- or triethanolamine.

The dyes of formula (1) or (2) are present in the novel dye mixture e.g.in a weight ratio from 10:90 to 90:10, preferably from 20:80 to 80:20and, particularly preferably, from 25:75 to 75:25.

The novel reactive dye mixtures are suitable for dyeing and printing avery wide range of materials, such as silk, leather, wool, polyamidefibres and polyurethanes and, in particular, cellulosic fibre materialsof all kinds. Such fibre materials are, for example, the naturalcellulose fibres, such as cotton, linen and hemp, and cellulose andregenerated cellulose, e.g. viscose, and also modal fibres and theirmixtures with cotton. The reactive dye mixtures are also suitable fordyeing or printing hydroxyl group-containing fibres present in blends,for example blends of cotton with polyamide fibres or, in particular,with polyester fibres.

In another of its aspects, this invention accordingly relates to aprocess for dyeing or printing hydroxyl group-containing ornitrogen-containing fibre materials with the novel dye mixtures,preferably cellulosic fibre materials and, in particular,cotton-containing fibre materials.

The novel dye mixtures can be applied to and fixed on the fibre materialin different manner, in particular in the form of aqueous dye solutionsand printing pastes. They are suitable both for the exhaust process andfor dyeing by the pad-dyeing process, in which the goods are impregnatedwith aqueous and optionally saline dye solutions and the dyes are fixedafter treatment with alkali or in the presence of alkali, wherenecessary with heating. After fixing, the dyeings or prints arethoroughly rinsed with cold and hot water, if required with addition ofa dispersant which promotes the diffusion of the unfixed components.

The novel reactive dye mixtures are distinguished by high reactivity,good fixation and excellent build-up. They can therefore be used by theexhaust process at low dyeing temperatures and require only shortsteaming times in the pad-steam process. The degrees of fixation arehigh and the unfixed components can be easily washed off, the differencebetween degree of exhaustion and degree of fixation being remarkablysmall, i.e. the soap loss is very small. The reactive dye mixtures arealso particularly suitable for printing, especially cotton, but also forprinting nitrogen-containing fibres, e.g. wool or silk or blendscontaining wool or silk.

The dyeings and prints obtained using the novel dye mixtures have hightinctorial strength and high fibre-dye bond stability both in the acidand in the alkaline range, as well as good light fastness and very goodwetfastness properties, such as fastness to washing, water, seawater,cross-dyeing and perspiration, and good fastness to pleating, ironingand rubbing.

The following Examples illustrate the invention in more detail.Temperatures are given in degrees Celsius and parts and percentages areby weight, unless otherwise stated. The ratio of parts by weight toparts by volume is the same as that of the kilogramme to the liter.

EXAMPLE 1

10.1 parts of the monoazo compound which, in the from of the free acid,corresponds to formula (101)

and 11.1 parts of the monoazo compound which, in the form of the freeacid, corresponds to formula (102)

are stirred in 120 parts of water and adjusted to pH 6.5 to 7 with 1 Nof HCl. The resulting solution is slowly added dropwise to a 0 to 5° C.cool suspension of 17.8 parts of the compound of formula (103)

(obtained by condensing cyanuric fluoride with4-(β-sulfatoethylsulfonyl)aniline) at pH 4.2. During the dropwiseaddition, the pH is slowly increased to 6 with 2 N of NaOH and thetemperature is allowed to rise to 5 to 10° C. The mixture is stirredfirst for about one hour at 5 to 10° C. and then for about 20 hours atroom temperature.

The reaction mixture is then adjusted to pH 11 with 15% NaOH and isstirred for one hour at room temperature. The pH of the reaction mixtureis then adjusted to about 7 with 1N of HCl and the solution is freedfrom salt by dialysis. Concentration by evaporation yields 40.9 parts ofa dye mixture which contains the dyes of formulae (104) and (105)

shown here in the form of their salts, in a weight ratio from 48.5:51.5.The dye mixture so obtained dyes cotton in an orange shade.

If the procedure of Example 1 is reversed by dropwise addition of the 0to 5° C. cool suspension of the compound of formula (103) to the mixtureof the monoazo compounds which, in the form of the free acid, correspondto formulae (101) and (102), then a dye mixture is like-wise obtainedwhich contains the dyes of formulae (104) and (105) shown here in theform of the free acid.

EXAMPLE 2

The procedure of Example 1 is repeated, but replacing the 10.1 parts ofthe compound of formula (101) with an equimolar amount of the compoundof formula (106)

which yields a dye mixture containing the dyes of formulae (105) and(107)

shown here in the form of the free acid, in a weight ratio from 49:51.The dye mixture so obtained dyes cotton in an orange shade.

EXAMPLE 3

The procedure of Example 1 is repeated, but replacing the 17.8 parts ofthe compound of formula (103) with an equimolar amount of the compoundof formula (108)

(obtained by condensing cyanuric chloride with4-(β-sulfatoethylsulfonyl)aniline), which yields a dye mixturecontaining the dyes of formulae (109) and (110)

shown here in the form of the free acid, in a weight ratio from 49:51.The dye mixture so obtained dyes cotton in an orange shade.

EXAMPLES 4 TO 6

In general analogy to the instructions of Example 1, dye mixtures may beobtained containing dyes of the following general formulae (I) and (II)

shown here in the form of the free acid, in the cited weight ratio, D,R₃ and X each having the meanings given in Table 1. These dye mixturesdye cotton in the cited shades.

TABLE 1 Ex. D R₃ X (I):(II) Shade 4

CH₃ Cl 49:51 orange 5

OCH₃ F 62.5:37.5 scarlet 6

OCH₃ Cl 63:37 scarlet

EXAMPLES 7 TO 12

In general analogy to the instructions of Example 1, dye mixtures may beobtained containing dyes of the following general formulae (III) and(IV)

shown here in the form of the free acid, in the cited weight ratio, D,R₃ and X each having the meanings cited in Table 2, if the compound offormula (103) is replaced with a compound of the general formula (V)

(obtained by condensing cyanuric fluoride (X═F) or cyanuric chloride(X═Cl) with an amine of formula

wherein X is F or Cl. These dye mixtures dye cotton in the cited shades.

TABLE 2 Ex. D R₃ X (III):(IV) Shade  7

H Cl 50:50 orange  8

H F 50:50 orange  9

CH₃ Cl 50:50 orange 10

CH₃ F 50:50 orange 11

OCH₃ F 61:39 scarlet 12

OCH₃ Cl 62:38 scarlet

EXAMPLES 13 TO 16

In general analogy to the instructions of Example 1, dye mixtures may beobtained containing dyes of the following general formulae (V) and (VI)

shown here in the form of the free acid, in the cited weight ratio, D,R₃ and X each having the meanings given in Table 3, if the compound offormula (103) is replaced with a compound of the general formula (VII)

(obtained by condensing cyanuric fluoride (X═F) or cyanuric chloride(X═Cl) with an amine of formula H₂N—(CH₂)₂—O—(CH₂)₂—SO₂—(CH₂)₂—Cl),wherein X is F or Cl. These dye mixtures dye cotton in the cited shades.

TABLE 3 Ex. D R₃ X (V):(VI) Shade 13

H Cl 50:50 orange 14

H F 50:50 orange 15

CH₃ Cl 50:50 orange 16

OCH₃ Cl 62:38 scarlet

Dyeing Instructions

2 parts of the reactive dye mixture obtained according to Example 1 aredissolved in 400 parts of water. To this solution are added 1500 partsof a solution which contains 51 g/l of sodium chloride. 100 parts ofcotton fabric are put into this dyebath at 60° C. and, after 45 minutesat 60° C., 100 parts of a solution containing 16 g/l of sodium hydroxideand 20 g of calcined sodium carbonate are added. Dyeing is continued foranother 45 minutes at this temperature. The dyed goods are then rinsed,soaped at the boil for a quarter of an hour with a non-ionic detergent,rinsed again and dried.

As an alternative to the above instruction, it is possible to dye not at60° C. but at 70° C. or 80° C.

Printing Procedure

3 parts of the reactive dye mixture obtained according to Example 1 aresprinkled, with rapid stirring, into 100 parts of a stock thickeningwhich contains 50 parts of 5% sodium alginate thickening, 27.8 parts ofwater, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and1.2 parts of sodium hydrogen carbonate. A cotton fabric is printed withthe printing paste so obtained and dried. The printed fabric is steamedfor 2 minutes at 102° C. in saturated steam, then rinsed, if necessarysoaped at the boil, then rinsed once more and subsequently dried.

What is claimed is:
 1. A dye mixture, which comprises at least one dyeof formula (1)

together with at least one dye of formula (2)

wherein R₁, R₂, R₄ and R₅ are each independently of one another hydrogenor unsubstituted or substituted C₁-C₄alkyl, (R₃)₀₋₂ is 0 to 2 identicalor different substituents selected from the group consisting of halogen,C₂-C₄alkanoylamino, C₁-C₄alkyl and C₁-C₄alkoxy, A₁ and A₂ are eachindependently of the other an unsubstituted or substituted phenyleneradical or a C₁-C₈alkylene radical which may be interrupted by oxygen, Dis a radical of formula (3) or (4)

 wherein (R₆)₀₋₂ is 0 to 2 identical or different substituents selectedfrom the group consisting of halogen, C₂-C₄alkanoylamino, C₁-C₄alkyl andC₁-C₄alkoxy, X₁ and X₂ are halogen, and Y₁ and Y₂ are each independentlyof the other a fibre-reactive radical of formula (5a), (5b), (5c) or(5d) —SO₂—Z  (5a), —CONH—(CH₂)_(m)—SO₂—Z  (5b),—NH—CO—CH(Hal)—CH₂Hal  (5c) or —NH—CO—C(Hal)═CH₂  (5d),  wherein m isthe number 2, 3 or 4, Hal is halogen, and Z is vinyl or a radical—CH₂—CH₂—U, and U is a group which may be split off with alkali.
 2. Adye mixture according to claim 1, wherein R₁, R₂, R₄ and R₅ are eachindependently of one another hydrogen or C₁-C₄-alkyl.
 3. A dye mixtureaccording to claim 1, wherein D defined as a radical of formula (3) is aradical of formula (3a)

and, defined as a radical of formula (4), is a radical of formula (4a)

 wherein R₆ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxy.
 4. A dye mixtureaccording to claim 1, wherein X₁ and X₂ are each independently of theother fluoro or chloro.
 5. A dye mixture according to claim 1, wherein Uis —Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅,—OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂.
 6. A dye mixture according toclaim 5, wherein U is —Cl or —OSO₃H.
 7. A dye mixture according to claim1, wherein the radicals of formulae —A₁—Y₁ and A₂—Y₂ are eachindependently of the other a radical of formula (6a), (6b) or (6c)

wherein (R₇)₀₋₂ is 0 to 2 identical or different substituents selectedfrom the group consisting of sulfo, methyl and methoxy, Y isα,β-dibromopropionylamino or α-bromoacryloylamino, and Z₁ and Z₂ areeach independently of the other vinyl, β-chloroethyl or β-sulfatoethyl.8. A dye mixture according to claim 7, wherein the radicals of formulae—A₁—Y₁ and A₂—Y₂ are each independently of the other a radical offormula (6a) or (6b).
 9. A dye mixture according to claim 1, whichcomprises at least one dye of formula (1a)

together with at least one dye of formula (2a)

 wherein R₃ is hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy, D is a radical offormula (3a) or (4a)

 wherein R₆ is hydrogen, C₁-C₄alkyl or C₁-C₄alkoxy, X₁ and X₂ are eachindependently of the other fluoro or chloro, and —A₁—Y₁ and A₂—Y₂ areeach independently of the other a radical of formula (6a) or (6b)

 wherein (R₇)₀₋₂ is 0 to 2 identical or different substituents selectedfrom the group consisting of sulfo, methyl or methoxy, and Z₁ and Z₂ areeach independently of the other vinyl, β-chloroethyl or β-sulfatoethyl.10. A dye mixture according to claim 9, which comprises at least one dyeof formula (1b)

together with at least one dye of formula (2b)

 wherein R₃ is hydrogen or methyl, and X₁ and X₂ and —A₁—Y₁ and A₂—Y₂each have the meanings defined in claim
 9. 11. A dye mixture accordingto claim 9, which comprises at least one dye of formula (1c)

together with at least one dye of formula (2c)

 wherein X₁ and X₂ and —A₁—Y, and A₂—Y₂ each have the meanings definedin claim
 9. 12. A process for the preparation of a dye mixture accordingto claim 1, which comprises reacting a compound of formula

and a compound of formula

 with cyanuric halide and an amine selected from the group consisting offormulae (9) and (10)

 in any sequence, R₁, R₂, R₃, R₄, R₅, A₁, A₂, D, Y₁ and Y₂ having themeanings defined in claim
 1. 13. A method of dyeing or printing hydroxylgroup-containing or nitrogen-containing fibre materials, which comprisescontacting the materials with a tinctorially effective amount of a dyemixture according to claim
 1. 14. A method according to claim 13,wherein the hydroxyl group-containing fibre materials are cellulosicfibre materials.
 15. A method according to claim 14, wherein thecellulosic fibre materials are cotton-containing fibre materials.